EP2658919B1 - Composition de vulcanisat thermoplastique, son procédé de production, et articles fabriqués à partir de celle-ci - Google Patents

Composition de vulcanisat thermoplastique, son procédé de production, et articles fabriqués à partir de celle-ci Download PDF

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Publication number
EP2658919B1
EP2658919B1 EP10861392.8A EP10861392A EP2658919B1 EP 2658919 B1 EP2658919 B1 EP 2658919B1 EP 10861392 A EP10861392 A EP 10861392A EP 2658919 B1 EP2658919 B1 EP 2658919B1
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Prior art keywords
propylene
thermoplastic vulcanizate
based polymer
vulcanizate composition
component
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German (de)
English (en)
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EP2658919A4 (fr
EP2658919A1 (fr
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Sam Yabin SUN
Morgan Hughes
Xiangyang Tai
Arnis Paeglis
Gary Robert Marchand
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Dow Global Technologies LLC
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Dow Global Technologies LLC
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/16—Elastomeric ethene-propene or ethene-propene-diene copolymers, e.g. EPR and EPDM rubbers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/10—Homopolymers or copolymers of propene
    • C08L23/12—Polypropene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/10—Homopolymers or copolymers of propene
    • C08L23/14—Copolymers of propene
    • C08L23/142—Copolymers of propene at least partially crystalline copolymers of propene with other olefins
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/26—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers modified by chemical after-treatment
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
    • C08K5/0025—Crosslinking or vulcanising agents; including accelerators
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/22—Mixtures comprising a continuous polymer matrix in which are dispersed crosslinked particles of another polymer
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2312/00—Crosslinking

Definitions

  • the instant invention relates to a thermoplastic vulcanizate composition, method of producing the same, articles made therefrom, and methods for making such articles.
  • TPO-based materials offer improved recyclability and sealability over commercial XL-EPDM materials. TPO-based materials, however, generally offer poor low temperature flexibility.
  • Thermoplastic Vulcanizate (TPV) materials including XL-EPDM dispersed in a TPO polymeric matrix wherein the XL-EPDM has a particle size of several micrometers (microns), have been developed for use in roofing membranes.
  • the TPO matrix may, in some instances, be a polypropylene (PP) in which the XL-EPDM interpolymer is miscible.
  • TPV materials provide both the recyclability and sealability of TPO-based materials and the good low temperature flexibility of XL-EPDM materials.
  • thermoplastic vulcanizates Although numerous types of thermoplastic vulcanizates are known, there is still a need for further improvements on thermoplastic materials having good elastomeric properties. Specifically, there is a need for a method to produce thermoplastic vulcanizate with improved tensile strength, elongation, tear strength and processability.
  • the instant invention is a thermoplastic vulcanizate composition, method of producing the same, articles made therefrom, and methods for making such articles.
  • the instant invention provides a thermoplastic vulcanizate composition
  • a thermoplastic vulcanizate composition comprising: from 5 wt% to 95 wt%, based on the total weight of the thermoplastic vulcanizate composition, of a first component comprising a first propylene-based polymer selected from the group consisting of (i) propylene/a-olefin copolymers comprising from 1 to 20 wt% ⁇ -olefin and characterized by a g' ratio of less than1, measured at interpolymer number average molecular weight (Mn), an MFR (2.16kg @ 230°C) greater than or equal to 0.01, a density greater than or equal to 0.850 g/cc, and a molecular weight distribution, Mw/Mn, less than or equal to 3.5, and (ii) combinations thereof, and from 5 wt% to 95 wt%, based on the total weight of the thermoplastic vulcanizate composition, of a second component selected from the group consisting of
  • the instant invention further provides a process for making a thermoplastic vulcanizate composition
  • a first component comprising a first propylene-based polymer selected from the group consisting of (i) propylene/a-olefin copolymers comprising from 1 to 20 wt% ⁇ -olefin and characterized by a g' ratio of less than1, measured at interpolymer number average molecular weight (Mn), an MFR (2.16kg @ 230°C) greater than or equal to 0.01, a density greater than or equal to 0.850 g/cc, and a molecular weight distribution, Mw/Mn, less than or equal to 3.5, and (ii) combinations thereof; selecting a second component selected from the group consisting of curable or vulcanizable rubbers, having a density from 0.85 to 0.88 g/cc, I 2 from 0.001 to 5 g/10 min, and a Mooney viscosity from 5 to 400, and combinations thereof; wherein
  • the instant invention further provides an article comprised of one or more thermoplastic vulcanizate compositions of any one of the preceding embodiments.
  • the instant invention provides a composition, method of producing the same, and articles made therefrom, in accordance with any of the preceding embodiments, except that the second component comprises an ethylene-propylene-diene monomer interpolymer.
  • the instant invention provides a composition, method of producing the same, and articles made therefrom, in accordance with any of the preceding embodiments, except that the thermoplastic vulcanizate composition further comprises from greater than 0 wt% to 50 wt%, based on the total weight of the thermoplastic vulcanizate composition, of a third component comprising a second propylene-based polymer having a melting temperature greater than 120 °C and selected from the group consisting of (i) propylene homopolymers, (ii) propylene- ⁇ -olefin interpolymers comprising at least 80 wt% propylene, and (iii) combinations thereof.
  • the instant invention provides a composition, method of producing the same, and articles made therefrom, in accordance with any of the preceding embodiments, except that the thermoplastic vulcanizate composition further comprises from greater than 0 wt% to 2 wt%, based on the total weight of the thermoplastic vulcanizate composition, of a fourth component selected from the group consisting of phenolic resins, peroxides, maleimides, silicon-containing azides, and combinations thereof.
  • the instant invention provides a composition, method of producing the same, and articles made therefrom, in accordance with any of the preceding embodiments, except that the thermoplastic vulcanizate composition according further comprises one or more additives selected from the group consisting of, colored pigments, stabilizers, antidegradants, flame retardants, processing aids, adhesives, tackifiers, plasticizers, waxes, and discontinuous fibers.
  • the thermoplastic vulcanizate composition according further comprises one or more additives selected from the group consisting of, colored pigments, stabilizers, antidegradants, flame retardants, processing aids, adhesives, tackifiers, plasticizers, waxes, and discontinuous fibers.
  • the instant invention provides a composition, method of producing the same, and articles made therefrom, in accordance with any of the preceding embodiments, except that the thermoplastic vulcanizate composition further comprises one or more fillers.
  • the instant invention provides a composition, method of producing the same, and articles made therefrom, in accordance with any of the preceding embodiments, except that the process further comprises: selecting a third component comprising a second propylene-based polymer selected from the group consisting of (i) propylene homopolymers, (ii) propylene- ⁇ -olefin interpolymers comprising at least 80 wt% propylene, and (iii) combinations thereof; and mixing the third component with the first and second components under the dynamic vulcanization conditions.
  • a third component comprising a second propylene-based polymer selected from the group consisting of (i) propylene homopolymers, (ii) propylene- ⁇ -olefin interpolymers comprising at least 80 wt% propylene, and (iii) combinations thereof.
  • the instant invention provides a composition, method of producing the same, and articles made therefrom, in accordance with any of the preceding embodiments, except that the process further comprises: selecting a fourth component selected from the group consisting of phenolic resins, peroxides, maleimides, silicon-containing azides, and combinations thereof; and mixing the fourth component with the first and second components under the dynamic vulcanization conditions.
  • the instant invention provides a composition, method of producing the same, and articles made therefrom, in accordance with any of the preceding embodiments, except that the first propylene-based polymer has a g' ratio of less than 0.85, measured at interpolymer number average molecular weight (Mn.).
  • the instant invention provides a composition, method of producing the same, and articles made therefrom, in accordance with any of the preceding embodiments, except that the first propylene-based polymer has a g' ratio of less than 0.80, measured at interpolymer number average molecular weight (Mn.).
  • the instant invention provides a composition, method of producing the same, and articles made therefrom, in accordance with any of the preceding embodiments, except that the first propylene-based polymer comprises at least 80 weight percent (wt %) units derived from propylene, and between 1 and 20 wt % units derived from ethylene.
  • the instant invention provides a composition, method of producing the same, and articles made therefrom, in accordance with any of the preceding embodiments, except that the first propylene-based polymer is characterized by a relative compositional drift of less than 50%.
  • the instant invention provides a composition, method of producing the same, and articles made therefrom, in accordance with any of the preceding embodiments, except that the first propylene-based polymer is characterized by a relative compositional drift of less than 40%.
  • the instant invention provides a composition, method of producing the same, and articles made therefrom, in accordance with any of the preceding embodiments, except that the first propylene-based polymer is characterized by a propylene chain segments having a chain isotacticity triad index of at least 70 mole percent.
  • the instant invention provides a composition, method of producing the same, and articles made therefrom, in accordance with any of the preceding embodiments, except that the first propylene-based polymer is characterized by a propylene chain segments having a chain isotacticity triad index of at least 80 mole percent.
  • the instant invention provides a thermoplastic vulcanizate composition, method of producing the same, articles made therefrom, and method of making such articles, in accordance with any of the preceding embodiments, except that the thermoplastic vulcanizate composition further comprises one or more oils.
  • the instant invention provides a thermoplastic vulcanizate composition, method of producing the same, articles made therefrom, and method of making such articles, in accordance with any of the preceding embodiments, except that the articles are weatherstripping, flexible rubber goods, such as constant velocity joint sleeves, foams, such as shoe foams and under dash interior car applications, and wire and cable jacketing.
  • the instant invention provides a thermoplastic vulcanizate composition consisting essentially of: from 5 wt% to 95 wt%, based on the total weight of the thermoplastic vulcanizate composition, of a first component comprising a first propylene-based polymer selected from the group consisting of (i) propylene/a-olefin copolymers comprising from 1 to 20 wt% ⁇ -olefin and characterized by a g' ratio of less than1, measured at interpolymer number average molecular weight (Mn), an MFR (2.16kg @ 230°C) greater than or equal to 0.01, a density greater than or equal to 0.850 g/cc, and a molecular weight distribution, Mw/Mn, less than or equal to 3.5, and (ii) combinations thereof, and from 5 wt% to 95 wt%, based on the total weight of the thermoplastic vulcanizate composition, of a second component selected from the group consisting of curable or vulcanizate composition
  • Polymer means a polymeric compound prepared by polymerizing monomers, whether of the same or a different type.
  • the generic term “polymer” embraces the terms “homopolymer,” “copolymer,” “terpolymer” as well as “interpolymer.”
  • Interpolymer means a polymer prepared by the polymerization of at least two different types of monomers.
  • the generic term “interpolymer” includes the term “copolymer” (which is usually employed to refer to a polymer prepared from two different monomers) as well as the term “terpolymer” (which is usually employed to refer to a polymer prepared from three different types of monomers). It also encompasses polymers made by polymerizing four or more types of monomers.
  • the instant invention is a thermoplastic vulcanizate composition, process of producing the same, and articles made therefrom.
  • thermoplastic vulcanizate composition comprises: from 5 wt% to 95 wt%, based on the total weight of the thermoplastic vulcanizate composition, of a first component comprising a first propylene-based polymer selected from the group consisting of (i) propylene/a-olefin copolymers comprising from 1 to 20 wt% ⁇ -olefin and having a g' ratio of less than 1, measured at interpolymer number average molecular weight (Mn), an MFR (2.16kg @ 230°C) greater than or equal to 0.01 g/10 min, a density greater than or equal to 0.850 g/cc, and molecular weight distribution, Mw/Mn, less than 4, and (ii) combinations thereof, and from 5 wt% to 95 wt%, based on the total weight of the thermoplastic vulcanizate composition, of a second component selected from the group consisting of curable or vulcanizable rubbers, having a density from 0.85
  • thermoplastic vulcanizate composition comprises: from 5 wt% to95 wt%, based on the total weight of the thermoplastic vulcanizate composition, of a first component selected from the group consisting of (i) propylene/a-olefin copolymer having a MFR (2.16kg @ 230°C) greater than or equal to 0.01 g/10 min, a density greater than or equal to 0.850 g/cc, molecular weight distribution, Mw/Mn, less than 4, a narrow co-monomer distribution; and comprising from 1 to 20 wt% ⁇ -olefin, based on the total weight of the propylene/ ⁇ -olefin copolymer, and (ii) combinations thereof.
  • a first component selected from the group consisting of (i) propylene/a-olefin copolymer having a MFR (2.16kg @ 230°C) greater than or equal to 0.01 g/10 min, a density greater than or equal to 0.850
  • weight percent of the first component can be from a lower limit of 5, 10, 20, 40, 60, 80 or 90 weight percent to an upper limit of 10, 30, 50, 70, 90 or 95 weight percent.
  • the amount of the first component in the thermoplastic vulcanizate composition may be in the range of from 5 to 95 weight percent, or in the alternative, the amount of the first component in the thermoplastic vulcanizate composition may be in the range of from 5 to 75 weight percent, or in the alternative, the amount of the first component in the thermoplastic vulcanizate composition may be in the range of from 5 to 50 weight percent, or in the alternative, the amount of the first component in the thermoplastic vulcanizate composition may be in the range of from 10 to 50 weight percent, or in the alternative, the amount of the first component in the thermoplastic vulcanizate composition may be in the range of from 10 to 40 weight percent, or in the alternative, the amount of the first component in the thermoplastic vulcanizate composition may be in the range of from 15 to 60 weight percent.
  • the First Component first propylene-basedpolymer
  • Propylene/ ⁇ -olefin copolymers useful as the first propylene-based polymer has a g' ratio of less than1, measured at interpolymer number average molecular weight (Mn).
  • the g' ratio is the ratio of the intrinsic viscosity (IV) value for the branched propylene-ethylene copolymer divided by the intrinsic viscosity value for the linear propylene-ethylene copolymer having similar ethylene content, i.e., polymer density, and similar molecular weight, i.e., melt flow rate.
  • Similar means within twenty percent (20%) of each value.
  • the g' ratio of the first propylene-based polymer can be from an upper limit of 0.99, 0.95, 0.90, 0.85 or 0.8.
  • the first propylene-based polymer comprises an average of at least 0.001 long chain branches per 1000 total carbons. All individual values and sub-ranges from at least 0.001 long chain branches per 1000 total carbons are included herein and disclosed herein; for example, the level of long chain branching in the first propylene-based polymer can be from a lower limit of 0.001 long chain branches per 1000 total carbons, 0.005 long chain branches per 1000 total carbons, 0.01 long chain branches per 1000 total carbons, or 0.05 long chain branches per 1000 total carbons.
  • the first propylene-based polymer comprises an average of no more than 3 long chain branches per 1000 total carbons. All individual values and sub-ranges up to no more than 3 long chain branches per 1000 total carbons are included herein and disclosed herein; for example, the level of long chain branching in the p first propylene-based polymer can be from an upper limit of 3 long chain branches per 1000 total carbons, 2 long chain branches per 1000 total carbons, 1 long chain branch per 1000 total carbons, 0.1 long chain branches per 1000 total carbons, 0.01 long chain branches per 1000 total carbons, or 0.001 long chain branches per 1000 total carbons.
  • Long chain branching means a chain length greater than that resulting from the incorporation of the comonomer into the polymer backbone.
  • a propylene/1-octene interpolymer of this invention has backbones with long chain branches of at least seven (7) carbons n length, but these backbones also have short chain branches of only six (6) carbons in length.
  • a propylene/1-hexene interpolymer of this invention will have long chain branches of at least five (5) carbons in length but shore chain branches of only four (4) carbons in length.
  • the first propylene-based polymers may, in some embodiments, have a weight average molecular weight, Mw, from 10,000 to 5,000,000 g/mole. All individual values and subranges from 10,000 to 5,000,000 g/mole are included herein and disclosed herein; for example, the Mw of the first propylene-based polymer can be from a lower limit of 10,000; 40,000; 80,000; 200,000; 300,000; or 4,000,000 g/mole to an upper limit of 40,000; 80,000; 200,000; 300,000; or 5,000,000 g/mole.
  • the Mw of the first propylene-based polymer may be in the range of from 10,000 to 5,000,000 g/mole, or in the alternative, the Mw of the first propylene-based polymer may be in the range of from 40,000 to 300,000 g/mole, or in the alternative, the Mw of the first propylene-based polymer may be in the range of from 80,000 to 200,000 g/mole.
  • the first propylene-based polymers have an MFR (2.16kg @ 230°C) greater than or equal to 0.01 g/10 min. All individual values and sub-ranges from greater than or equal to 0.01 g/10 min are included herein and disclosed herein; for example, the MFR of the first propylene-based polymer can be from a lower limit of 0.01, 0.05, 0.1, 0.5, 1, 10, or 50 g/10 min, to an upper limit of 0.05, 0.1, 1, 10, 50, 80, or 100 g/10 min.
  • the MFR of the first propylene-based polymer may be in the range of from 0.01 to 100 g/10 min, or in the alternative, the MFR of the first propylene-based polymer may be in the range of from 0.05 to 80 g/10 min, or in the alternative, the MFR of the first propylene-based polymer may be in the range of from 0.1 to 50 g/10 min or in the alternative, the MFR of the first propylene-based polymer may be in the range of from 0.5 to 50 g/10 min.
  • the first propylene-based polymers have a density greater than or equal to 0.850 g/cc. All individual values and sub-ranges from greater than or equal to 0.850 g/cc. are included herein and disclosed herein; for example, the density of the first propylene-based polymer can be from a lower limit of 0.850 g/cc, 0.86 g/cc, 0.865 g/cc, 0.89 g/cc, 0.9 g/cc, or 0.91 g/cc to an upper limit of 0.86 g/cc, 0.865 g/cc, 0.89 g/cc, 0.9 g/cc, 0.91 g/cc, or 0.915 g/cc.
  • the density of the first propylene-based polymer may be in the range from 0.85 to 0.90 g/cc, or in the alternative, the density of the first propylene-based polymer may be in the range from 0.86 to 0.89 g/cc, density of the first propylene-based polymer may be in the range from 0.865 to 0.90 g/cc.
  • the first propylene-based polymer has a molecular weight distribution, Mw/Mn, (MWD) (abs), less than or equal to 3.5. All individual values and sub-ranges from less than 3.5 are included herein and disclosed herein; for example, the Mw/Mn of the propylene/ ⁇ -olefin copolymers can be from a lower limit of 1.5, 2, 2.5 or 3 to an upper limit of 2, 2.5, 3 or 3.5.
  • the MWD of the first component may be in the range of from1.5 to 3.5, or in the alternative, the MWD of the first component may be in the range of from 2 to 3, or in the alternative, the MWD of the first component may be in the range of from 2.5 to 3.5, or in the alternative, the MWD of the first component may be in the range of from 3 to 3.5.
  • the first propylene-based polymer is characterized by propylene chain segments having a chain isotacticity triad index of at least 70 mole percent. All individual values and subranges from at least 70 mole percent are included herein and disclosed herein.
  • the first propylene-based polymer are characterized by propylene chain segments having a chain isotacticity triad index of at least 80 mole percent, or in the alternative, the first propylene-based polymer are characterized by propylene chain segments having a chain isotacticity triad index of at least 90 mole percent, or in the alternative, the first propylene-based polymer are characterized by propylene chain segments having a chain isotacticity triad index of at least 95 mole percent.
  • Propylene/a-olefin copolymers useful as the first propylene-based polymer have a narrow co-monomer distribution and comprise from 1 to 20 wt% ⁇ -olefin, based on the total weight of the propylene/ ⁇ -olefin copolymer. All individual values and sub-ranges from 1 to 20 wt% are included herein and disclosed herein; for example, the first propylene-based polymer can have a weight percent of units derived from ⁇ -olefin from a lower limit of 1, 5, 10, or 15 weight percent to an upper limit of 5, 10, 15 or 20 weight percent.
  • the weight percent of the first propylene-based polymer derived from ⁇ -olefin may be in the range of from 1 to 20 weight percent, or in the alternative, the weight percent of the first propylene-based polymer derived from ⁇ -olefin may be in the range of from 10 to 20 weight percent, or in the alternative, the weight percent of the first propylene-based polymer derived from ⁇ -olefin may be in the range of from 15 to 20 weight percent, or in the alternative, the weight percent of the first propylene-based polymer derived from ⁇ -olefin may be in the range of from 5 to 15 weight percent.
  • the first propylene-based polymer has a narrow co-monomer distribution. In some embodiments of the invention, the first propylene-based polymer have a compositional drift of less than, or equal to, 50%. All individual values and subranges of less than, or equal to, 50% are included herein and disclosed herein. For example, the first propylene-based polymer copolymers may have a compositional drift of less than, or equal to, 50%, or in the alternative, the first propylene-based polymer may have a compositional drift of less than, or equal to, 40%.
  • Exemplary propylene/a-olefin copolymers useful as the first propylene-based polymer include those described in U.S. Published Application No. 20100285253 .
  • Propylene/a-olefin copolymers useful as the first propylene-based polymer may be made according to the methods and utilizing the catalyst systems described in U.S. Published Application No. 20100285253 .
  • the first propylene-based polymer is prepared by polymerizing propylene and ethylene using a hafnium metal complex and from 10 to 200 moles per mole of hafnium of an aluminoxane, under continuous, solution polymerization conditions at a temperature from 120 to 250°C, alternatively from 130 to 250°C, under high propylene conversion conditions (> 75% or in the alternative >80%) to prepare a polymer comprising, in polymerized form, from 1 to 20 weight percent units derived from ethylene.
  • the first propylene-based polymer may be prepared using a Group 4 metal complex of a bis (hydroxyarylaryloxy) ligand.
  • a Group 4 metal complex which may be used in preparing propylene- ⁇ -olefin copolymer useful in the invention is [[rel-2',2"'-[(1R,2R)-1,2-cyclohexanediylbis(methyleneoxy- ⁇ O)]bis[3-(9H-carbazol-9-yl)-5-methyl[1,1'-biphenyl]-2-olato-KO]](2-)]dimethyl hafnium and is depicted by the following structure, wherein the R groups are methyl groups:
  • the first propylene-based polymer may be produced using a metal complex depicted by the foregoing structure wherein R D independently each occurrence is chloro, methyl, or benzyl.
  • the metal complexes useful as catalysts in preparing the first propylene-based polymer useful in the inventive compositions may be prepared by standard metallation and ligand exchange procedures involving a source of the transition metal and a neutral polyfunctional ligand source.
  • the techniques employed may be the same as or analogous to those disclosed in, for example, U.S. Patent No. 6,827,976 and U.S. Patent Publication No. 20040010103 .
  • Exemplary first propylene-based polymer useful in the inventive compositions include VERSIFY 3000 and VERSIFY 3200, available from The Dow Chemical Company.
  • the first propylene-based polymer useful in the inventive thermoplastic vulcanizate compositions may comprise a combination of two or more embodiments as described herein.
  • the Second Component curable or vulcanizable rubbers
  • thermoplastic vulcanizate composition according to the present invention comprises from 5 wt% to 95 wt%, based on the total weight of the thermoplastic vulcanizate composition, of a second component selected from the group consisting of curable or vulcanizable rubbers, having a density from 0.85 to 0.88 g/cc, I 2 from 0.0001 to 5 g/10 min, and a Mooney viscosity from 5 to 400, and combinations thereof. All individual values and subranges from 5 to 95 weight percent of the second component are included herein and disclosed herein; for example, the weight percent of the second component can be from a lower limit of 5, 10, 20, 40, 60, 80 or 90 weight percent to an upper limit of 10, 30, 50, 70, 90 or 95 weight percent.
  • the amount of the second component in the thermoplastic vulcanizate composition may be in the range of from 5 to 95 weight percent, or in the alternative, the amount of the second component in the thermoplastic vulcanizate composition may be in the range of from 25 to 95 weight percent, or in the alternative, the amount of the second component in the thermoplastic vulcanizate composition may be in the range of from 50 to 95 weight percent, or in the alternative, the amount of the second component in the thermoplastic vulcanizate composition may be in the range of from 50 to 90 weight percent, or in the alternative, the amount of the second component in the thermoplastic vulcanizate composition may be in the range of from 60 to 90 weight percent, or in the alternative, the amount of the second component in the thermoplastic vulcanizate composition may be in the range of from 40 to 85 weight percent.
  • the second component useful in the inventive compositions, is selected from the group consisting of curable or vulcanizable rubber, and has a density from 0.85 to 0.88 g/cc. All individual values and subranges from 0.85 to 0.88 g/cc are included herein and disclosed herein; for example, the density of the second component can be from a lower limit of 0.85, 0.86, or 0.87 g/cc to an upper limit of 0.86, 0.87, or 0.88 g/cc.
  • the density of the second component in the thermoplastic vulcanizate composition may be in the range of from 0.85 to 0.88 g/cc, or in the alternative, the density of the second component in the thermoplastic vulcanizate composition may be in the range of from 0.86 to 0.88 g/cc, or in the alternative, the density of the second component in the thermoplastic vulcanizate composition may be in the range of from 0.87 to 0.88 g/cc.
  • the curable or vulcanizable rubbers useful in the second component in the inventive composition include both synthetic and natural rubbers and combinations thereof provided at least one of the rubbers is curable (i.e., crosslinkable) or vulcanizable.
  • Illustrative, non-limiting examples of rubbers include butyl rubber, halogenated butyl rubber, ethylene-propylene-diene rubber (EPDM), polyisoprene, polychloroprene, styrene-butadiene rubber, nitrile rubbers, and chlorosulfonated polyethylene.
  • the second component is selected from the group consisting of curable or vulcanizable rubbers having an I 2 from 0.001 to 5 g/10 min. All individual values and sub-ranges from 0.001 to 5 g/10 min are included herein and disclosed herein; for example, the I 2 of the second component can be from a lower limit of 0.001, 0.01, 0.1, 0.1, or 1 g/10 min to an upper limit of 0.01, 0.1, 1, or 5 g/10 min.
  • the I 2 of the second component in the thermoplastic vulcanizate composition may be in the range of from 0.001 to 5 g/10 min, or in the alternative, the I 2 of the second component in the thermoplastic vulcanizate composition may be in the range of from 0.001 to 0.01 g/10 min, or in the alternative, the I 2 of the second component in the thermoplastic vulcanizate composition may be in the range of from 0.1 to 1 g/10 min.
  • the second component useful in the inventive compositions, is selected from the group consisting of curable or vulcanizable rubber, has a Mooney viscosity [1 +4 @ 125°C] from 5 to 400. All individual values and sub-ranges from 5 to 400 are included herein and disclosed herein; for example, the Mooney viscosity [1 +4 @ 125°C] of the second component can be from a lower limit 5, 50, 100, 150, 200, 250, 300, or 350 to an upper limit of 50, 100, 150, 200, 250, 300, 350, or 400.
  • the Mooney viscosity [1 +4 @ 125°C] of the second component in the thermoplastic vulcanizate composition may be in the range of from 5 to 400, or in the alternative, the Mooney viscosity [1 +4 @ 125°C] of the second component in the thermoplastic vulcanizate composition may be in the range of from 100 to 200, or in the alternative, the Mooney viscosity [1 +4 @ 125°C] of the second component in the thermoplastic vulcanizate composition may be in the range of from 200 to 400.
  • Curable or vulcanizable rubbers useful in the inventive compositions may include any vulcanizable elastomer or rubber which is derived from at least an olefin, provided that the vulcanizable elastomer can be cross-linked (i.e., vulcanized) by a cross-linking agent.
  • the vulcanizable elastomer and the first component together can form a thermoplastic vulcanizate (TPV) after cross-linking.
  • TPV thermoplastic vulcanizate
  • Vulcanizable elastomers although generally thermoplastic in the uncured state, are normally classified as thermosets because they undergo an irreversible process of thermosetting to an unprocessable state.
  • the vulcanized elastomer is dispersed in a matrix of the thermoplastic polymer as domains.
  • the average domain size may range from 0.1 ⁇ m (micron) to 100 ⁇ m (micron), from 1 ⁇ m (micron) to 50 ⁇ m (microns); from 1 ⁇ m (micron) to 25 ⁇ m (microns); from 1 ⁇ m (micron) to 10 ⁇ m (microns), or from 1 ⁇ m (micron) to 5 ⁇ m (microns).
  • Non-limiting examples of suitable vulcanizable elastomers or rubbers include ethylene/higher ⁇ -olefin/polyene terpolymer rubbers such as EPDM. Any such terpolymer rubber which can be completely cured (cross-linked) with a phenolic curative or other cross-linking agent is satisfactory.
  • the terpolymer rubbers can be essentially non-crystalline, rubbery terpolymer of two or more alpha-olefins, preferably copolymerized with at least one polyene (i.e, an alkene comprises two or more carbon-carbon double bonds), usually a non-conjugated diene.
  • Suitable terpolymer rubbers comprise the products from the polymerization of monomers comprising two olefins having only one double bond, generally ethylene and propylene, and a lesser quantity of non-conjugated diene.
  • the amount of non-conjugated diene is usually from 2 to 10 weight percent of the rubber.
  • Any terpolymer rubber which has sufficient reactivity with phenolic curative to completely cure is suitable. The reactivity of terpolymer rubber varies depending upon both the amount of unsaturation and the type of unsaturation present in the polymer.
  • terpolymer rubbers derived from ethylidene norbornene are more reactive toward phenolic curatives than terpolymer rubbers derived from dicyclopentadiene and terpolymer rubbers derived from 1,4-hexadiene are less reactive toward phenolic curatives than terpolymer rubbers derived from dicyclopentadiene.
  • the differences in reactivity can be overcome by polymerizing larger quantities of less active diene into the rubber molecule.
  • ethylidene norbornene or dicyclopentadiene may be sufficient to impart sufficient reactivity to the terpolymer to make it completely curable with phenolic curative comprising conventional cure activators, whereas, at least 3.0 weight percent or more is required to obtain sufficient reactivity in an terpolymer rubber derived from 1,4-hexadiene.
  • Grades of terpolymer rubbers such as EPDM rubbers suitable for embodiments of the invention are commercially available. Some of the EPDM rubbers are disclosed in Rubber World Blue Book 1975 Edition, Materials and Compounding Ingredients for Rubber, pages 406-410 .
  • a terpolymer elastomer has an ethylene content of from 10% to 90% by weight, a higher alpha-olefin content of 10% to 80% by weight, and a polyene content of 0.5% to 20% by weight, all weights based on the total weight of the polymer.
  • the higher ⁇ -olefin contains from 3 to 14 carbon atoms. Examples of these are propylene, isobutylene, 1-butene, 1-pentene, 1-octene, 2-ethyl-1-hexene, 1-dodecene, and the like.
  • the polyene can be a conjugated diene such as isoprene, butadiene, chloroprene, and the like; a nonconjugated diene; a triene, or a higher enumerated polyene.
  • Examples of trienes are 1,4,9-decatriene, 5,8-dimethyl-1,4,9-decatriene, 4,9-dimethyl-1,4,9-decatriene, and the like.
  • the nonconjugated dienes are more preferred.
  • the nonconjugated dienes contain from 5 to 25 carbon atoms.
  • nonconjugated diolefins such as 1,4-pentadiene, 1,4-hexadiene, 1,5-hexadiene, 2,5-dimethyl-1,5-hexadiene, 1,4-octadiene, and the like; cyclic dienes such as cyclopentadiene, cyclohexadiene, cyclooctadiene, dicyclopentadiene, and the like; vinyl cyclic enes such as 1-vinyl-1-cyclopentene, 1-vinyl-1-cyclohexene, and the like; alkylbicyclo nondienes such as 3-methyl-bicyclo (4,2,1)nona-3,7-diene, 3-ethylbicyclonondiene, and the like; indenes such as methyl tetrahydroindene and the like; alkenyl norbornenes such as 5-ethylidene-2-norbornene, 5-butylidene-2
  • the terpolymer rubbers contain from 20% to 80% by weight of ethylene, 19% to 70% by weight of a higher ⁇ -olefin, and 1% to 10% by weight of a nonconjugated diene.
  • the more preferred higher ⁇ -olefins are propylene and 1-butene.
  • the more preferred polyenes are ethylidene norbornene, 1,4-hexadiene, and dicyclopentadiene.
  • the terpolymer rubbers have an ethylene content of from 50% to 70% by weight, a propylene content of from 20% to 49% by weight, and a nonconjugated diene content from 1% to 10% by weight, all weights based upon the total weight of the polymer.
  • terpolymer rubbers for use include NORDEL® IP 4770R, NORDEL® 3722 IP available from DuPont Dow Elastomers, Wilmington, Del. and KELTAN® 5636A available from DSM Elastomers Americas, Addis, La.
  • the Optional Third Component second propylene-based polymer
  • the inventive thermoplastic vulcanizate composition further comprises a third component comprising a second propylene-based polymer characterized by a melting temperature of greater than 120 °C and selected from the group consisting of (i) propylene homopolymers, (ii) propylene/a-olefin copolymers comprising at least 80 wt% propylene and (iii) combinations thereof.
  • the third component which may be included in some embodiments of the inventive composition, may be selected from the group consisting of homo-, impact, and random polymers of propylene, and combinations thereof.
  • the second propylene-based polymers useful in some embodiments of the inventive composition have a melting point greater than 120°C. All individual values and subranges from greater than 120°C are included herein and disclosed herein; for example, the melting point of the second propylene-based polymer can be from a lower limit of greater than 120 °C, or in the alternative, the melting point of the second propylene-based polymer can be greater than, or equal to 125 °C, or in the alternative, the melting point of the second propylene-based polymer can be greater than, or equal to 130 °C, or in the alternative, the melting point of the second propylene-based polymer can be greater than, or equal to 135 °C.
  • the optional second propylene-based polymer is a polypropylene homopolymer.
  • the polypropylene homopolymer has a melting point (Tm), as determined by DSC, greater than, or equal to, 125°C, or greater than, or equal to, 130°C, greater than, or equal to, 135°C, greater than, or equal to, 140°C.
  • Tm melting point
  • the polypropylene homopolymer has a heat of fusion ( ⁇ H f ), as determined by DSC, greater than, or equal to, 100 J/g, or greater than, or equal to, 80 J/g, greater than, or equal to, 85 J/g.
  • ⁇ H f heat of fusion
  • the polypropylene homopolymer has a weight average molecular weight (M w ) within the range having an upper limit of 5,000,000 g/mol, or 500,000 g/mol, and a lower limit of 10,000 g/mol, or 50,000 g/mol.
  • M w weight average molecular weight
  • the polypropylene homopolymer has a molecular weight distribution M w /M n (MWD), sometimes referred to as a "polydispersity index" (PDI), within the range having an upper limit of 40, or 30, or 20, or 10, and a lower limit of 2, or 3, or 4, or 5.
  • MWD molecular weight distribution
  • PDI polydispersity index
  • the third component in a preferred embodiment of the composition includes greater than or equal to 90 weight percent units derived from propylene with a remainder derived from olefins, particularly ethylene, and/or C 4 -C 10 ⁇ -olefins.
  • inventive compositions comprise a third component which comprises a second propylene-based polymer having a high MFR, namely from greater than 10 g/10 min to 40 g/10 min. All individual values and subranges from greater than 10 to 40 g/10 min are included herein and disclosed herein; for example, the MFR of the second propylene-based polymer can be from a lower limit of 10, 20, 30 or 35 g/10 min to an upper limit of 15, 20, 25, 30, 35, or 40 g/10 min.
  • the MFR of the second propylene-based polymer may be in the range of from 10 to 40 g/10 min, or in the alternative, the MFR of the second propylene-based polymer may be in the range of from 20 to 30 g/10 min, or in the alternative, the MFR of the second propylene-based polymer may be in the range of from 15 to 35 g/10 min.
  • the optional second propylene-based polymer may be present in an amount from 0 to 50 weight percent, based on the total weight of the thermoplastic vulcanizate composition. All individual values and subranges from 0 to 50 weight percent are included herein and disclosed herein; for example, the amount of the third component can be from a lower limit of 0, 10, 20, 30, or 40 weight percent to an upper limit of 10, 20, 30, 40, or 50 weight percent.
  • the amount of the third component may be in the range of from 0 to 50 weight percent, or in the alternative, the amount of the third component may be in the range of from 10 to 50 weight percent, the amount of the third component may be in the range of from 20 to 40 weight percent, the amount of the third component may be in the range of from 15 to 45 weight percent, the amount of the third component may be in the range of from 10 to 20 weight percent.
  • the second propylene-based polymer is a propylene/ ⁇ -olefin copolymer.
  • the propylene/ ⁇ -olefin copolymer comprises greater than or equal to 80 wt% units derived from propylene, based on the total weight of the propylene-/ ⁇ -olefin copolymer.
  • the propylene/ ⁇ -olefin copolymer may comprise amount of units derived from propylene from a lower limit of 80, 82, 84, 86, 88, 90, 92, 94, 96, 98 or 100 weight percent, based on the total weight of the propylene- ⁇ -olefin copolymer.
  • the third component is a propylene/ethylene copolymer.
  • the propylene/ethylene copolymer comprises greater than, or equal to, 80 wt%, or greater than, or equal to, 85 wt%, or greater than, or equal to, 90 wt%, or greater than, or equal to, 95 wt%, or greater than, or equal to, 98 wt% of polymerized propylene, based on the weight of the copolymer.
  • the propylene/ethylene copolymer comprises less than, or equal to, 10 wt%, or less than, or equal to, 8 wt%, or less than, or equal to, 6 wt%, or less than, or equal to, 4 wt%, or less than, or equal to, 2 wt% of polymerized ethylene, based on the weight of the copolymer.
  • the propylene/ethylene copolymer has a melting point (Tm), as determined by DSC, greater than, or equal to, 120°C, or greater than, or equal to, 125°C, greater than, or equal to, 130°C, greater than, or equal to, 140°C.
  • Tm melting point
  • the propylene/ethylene copolymer has a heat of fusion ( ⁇ H f ), as determined by DSC, greater than, or equal to, 75 J/g, or greater than, or equal to, 80 J/g, greater than, or equal to, 85 J/g.
  • ⁇ H f heat of fusion
  • the propylene/ethylene copolymer has a weight average molecular weight (M w ) within the range having an upper limit of 5,000,000 g/mol, or 500,000 g/mol, and a lower limit of 10,000 g/mol, or 50,000 g/mol.
  • M w weight average molecular weight
  • the second propylene-based polymers include, for example, those described in detail in the U.S. Patent Nos. 6,960,635 and 6,525,157 .
  • Such propylene/a-olefin copolymers are commercially available from The Dow Chemical Company, under the tradename VERSIFY Elastomers and Plastomers or from ExxonMobil Chemical Company, under the tradename VISTAMAXX.
  • exemplary second propylene-based polymers include random copolymer polypropylenes such as MOPLEN RP220 available from LyondellBasell and R352-08R available from The Dow Chemical.
  • the propylene homopolymer may be formed by the homopolymerization of propylene in a single stage or multiple stage reactors.
  • the propylene/ethylene copolymer may be formed by copolymerizing propylene and ethylene in a single stage or multiple stage reactors.
  • Polymerization methods for preparing the polypropylene homopolymer or propylene/ethylene copolymer include high pressure, slurry, gas, bulk, solution phase, and combinations thereof.
  • Catalyst systems include traditional Ziegler-Natta catalysts and single-site, metallocene catalyst systems. In one embodiment, the catalyst used has a high isospecificity.
  • Each polymerization may be carried out by a continuous or batch process, and may include the use of chain transfer agents, scavengers, or other such additives well-known to those skilled in the art.
  • the polypropylene homopolymer or propylene/ethylene copolymer may also contain one or more additives, such as flow improvers, nucleators, and antioxidants.
  • a third component useful in the inventive composition may comprise a combination of two or more embodiments as described herein.
  • the inventive thermoplastic vulcanizate composition further comprises from greater than 0 wt% to 2 wt%, based on the total weight of the thermoplastic vulcanizate composition, of a fourth component selected from the group consisting of curing agents and vulcanizing agents. All individual values and subranges from 0 to 2 weight percent are included herein and disclosed herein; for example, the amount of the optional fourth component in the inventive thermoplastic vulcanizates can be from a lower limit of 0, 0.1, 0.5, 1.0, or 1.5 weight percent to an upper limit of 0.1, 0.5, 1.0, 1.5, or 2.0 weight percent.
  • the amount of the fourth component in the inventive thermoplastic vulcanizates may be in the range of from 0 to 2 weight percent, or in the alternative, the amount of the optional fourth component in the inventive thermoplastic vulcanizates may be in the range of from 0.1 to 1.5 weight percent, or in the alternative, the amount of the optional fourth component in the inventive thermoplastic vulcanizates may be in the range of from 0.5 to 1.0 weight percent, or in the alternative, the amount of the optional fourth component in the inventive thermoplastic vulcanizates may be in the range of from 0.1 to 1.0 weight percent.
  • Illustrative curing agents include, but are not limited to, phenolic resins, peroxides, maleimides, and silicon-containing azides curatives. Depending on the rubber employed, certain curatives can be preferred. For example, where elastomeric copolymers containing units deriving from vinyl norbornene are employed, a peroxide curative can be preferred because the required quantity of peroxide will not have a deleterious impact on the engineering properties of the thermoplastic phase of the thermoplastic vulcanizate. In other situations, however, it can be preferred not to employ peroxide curatives because they can degrade the themoplastic components of the thermoplastic vulcanizate.
  • a preferred curing or vulcanizing agent is phenolic resin.
  • Other curing agents include, but are not limited to, peroxides, azides, aldehyde-amine reaction products, vinyl silane grafted moieties, hydrosilylation, substituted ureas, substituted guanidines; substituted xanthates; substituted dithiocarbamates; sulfur-containing compounds, such as thiazoles, imidazoles, sulfenamides, thiuramidisulfides, paraquinonedioxime, dibenzoparaquinonedioxime, sulfur; and combinations thereof. See Encyclopedia of Chemical Technology, Vol. 17, 2nd edition, Interscience Publishers, 1968 ; also Organic Peroxides, Daniel Seern, Vol. 1, Wiley-Interscience, 1970 ). Unless stated otherwise, the curing or vulcanizing agents described below require an elastomer containing a conjugated or non-conjugated diene.
  • Phenolic curing agents comprising methylol phenolic resins, halogen donor and metal compound are especially recommended, details of which are described in U.S. Pat. Nos. 3,287,440 and 3,709,840 .
  • Another suitable class of phenolic curing agents is disclosed in U.S. Pat. No. 5,952,425 .
  • Non-halogenated phenol curing resins are used in conjunction with halogen donors, preferably, along with a hydrogen halide scavenger.
  • halogenated, preferably brominated, phenolic resins containing from about 2 to about 10 weight percent bromine do not require a halogen donor but are used in conjunction with a hydrogen halide scavenger such as metal oxides such as iron oxide, titanium oxide, magnesium oxide, magnesium silicate, silicon dioxide and preferably zinc oxide, the presence of which promotes the cross-linking function of the phenolic resin; however, with rubbers which do not readily cure with phenolic resins, the conjoint use of a halogen donor and zinc oxide is recommended.
  • a hydrogen halide scavenger such as metal oxides such as iron oxide, titanium oxide, magnesium oxide, magnesium silicate, silicon dioxide and preferably zinc oxide
  • halogen donors are stannous chloride, ferric chloride, or halogen donating polymers such as chlorinated paraffin, chlorinated polyethylene, chlorosulfonated polyethylene, and polychlorobutadiene (neoprene rubber).
  • activator means any material which materially increases the cross-linking efficiency of the phenolic curing resin and includes metal oxides and halogen donors either used alone or conjointly.
  • Suitable phenolic curing resins and brominated phenolic curing resins are commercially available, for example, such resins may be purchased under the trade names SP-1045, CRJ-352, SP-1055 and SP-1056 from SI Group (Schenectady, New York). Similar functionally equivalent phenolic curing resins may be obtained from other suppliers.
  • Suitable peroxides as a curing agents include, but are not limited to, aromatic diacyl peroxides; aliphatic diacyl peroxides; dibasic acid peroxides; ketone peroxides; alkyl peroxyesters; alkyl hydroperoxides (for example, diacetylperoxide; dibenzoylperoxide; bis-2,4-dichlorobenzoyl peroxide; di-tert-butyl peroxide; dicumylperoxode; tert-butylperbenzoate; tert-butylcumylperoxide; 2,5-bis (t-butylperoxy)-2,5-dimethylhexane; 2,5-bis (t-butylperoxy)-2,5-dimethylhexyne-3; 4,4,4',4'-tetra-(t-butylperoxy)-2,2-dicyclohexylpropane; 1,4-bis-(t
  • Sulfur curing agents include, for example, sulfur, sulfur containing compounds, such as substituted guanidineds, substituted xanthates, substituted dithiocarbamates, thiazoles, imidazoles, sulfenamides, thiuramidisulfides, mixtures thereof and combinations thereof.
  • Silicon-containing curing agents generally include silicon hydride compounds having at least two SiH groups.
  • Silicon hydride compounds that are useful in practicing the present invention include, but are not limited to, methylhydrogen polysiloxanes, methylhydrogen dimethyl-siloxane copolymers, alkyl methyl polysiloxanes, bis(dimethylsilyl) alkanes, bis (dimethylsilyl) benzene, mixtures thereof and combinations thereof.
  • Suitable azide curing agents include, but are not limited to, azidoformates, such as tetramethylenebis(azidoformate), aromatic polyazides, such as 4,4'-diphenylmethane diazide; and sulfonazides, such as p,p'-oxybis(benzene sulfonyl azide). Additional azide curing agents are disclosed in U.S. Patent Nos. 3,284,421 ; and 3,297,674 .
  • a preferred class of azides is the poly(sulfonyl azide) described above.
  • the inventive thermoplastic vulcanizate composition further comprises a fifth component comprising a component selected from those additives conventional in the compounding of EPDM rubber, thermoplastic polymer resin and blends thereof.
  • a TPV may be modified, either before or after vulcanization, by addition of ingredients which are conventional in the compounding of EPDM rubber, thermoplastic polymer resin and blends thereof.
  • optional fifth components include particulate filler such as carbon black, amorphous precipitated or fumed silica, titanium dioxide, colored pigments, clay, talc, calcium carbonate, wollastonite, mica, montmorillonite, glass beads, hollow glass spheres, glass fibers, zinc oxide and stearic acid, stabilizers, antidegradants, flame retardants, processing aids, adhesives, tackifiers, plasticizers, wax, discontinuous fibers, such as wood cellulose fibers.
  • particulate filler such as carbon black, amorphous precipitated or fumed silica, titanium dioxide, colored pigments, clay, talc, calcium carbonate, wollastonite, mica, montmorillonite, glass beads, hollow glass spheres, glass fibers, zinc oxide and stearic acid, stabilizers, antidegradants, flame retardants, processing aids, adhesives, tackifiers, plasticizers, wax, discontinuous fibers, such as wood cellulose fibers.
  • Colorable compositions may be prepared by incorporation of non-black fillers instead of carbon black.
  • Colorless, off-white or white pigments such as amorphous precipitated or fumed silica, aluminum silicate, magnesium silicate, kaolin clay, montmorillonite, wollastonite, and titanium dioxide are suitable for such purposes.
  • thermoplastic vulcanizate composition further comprise an extender oil.
  • extender oils Any one or combination of known extender oils, including for example, naphthenic, aromatic or paraffinic oils, may optionally be used in the inventive composition. Additional useful extender oils are disclosed in Rubber World Blue Book, 1975 Edition, Materials and Compounding Ingredients for Rubber, pages 145-190 .
  • the quantity of extender oil added depends upon the properties desired, with the upper limit depending upon the compatibility of the particular oil and blend ingredients which limit is exceeded when excessive exuding of extender oil occurs. Typically, from 5 to 300 parts by weight extender oil are added per 100 parts by weight blend of olefin rubber and thermoplastic polymer resin.
  • extender oil from 30 to 250 parts by weight of extender oil are added per 100 parts by weight of rubber present in the blend with quantities of from 70 to 200 parts by weight of extender oil per 100 parts by weight of rubber being preferred.
  • the amount of extender oil depends, at least in part, upon the type of rubber. High viscosity rubbers are more highly oil extendable.
  • the inventive thermoplastic vulcanizate composition has a tensile strength at break of greater than or equal to 8 MPa. All individual values and sub-ranges from greater than or equal to 8 MPa are included herein and disclosed herein; for example, the tensile strength at break of the inventive composition can be from greater than or equal to 8, 9, or 10 MPa.
  • the inventive thermoplastic vulcanizate composition has a tensile strength at break of less than or equal to 50 MPa. All individual values and sub-ranges less than or equal to 50 MPa are included herein and disclosed herein; for example, the tensile strength at break of the inventive composition can be from less than or equal to 10, 20, 30,40 or 50 MPa.
  • the inventive thermoplastic vulcanizate composition has a tear strength at 23°C of greater than or equal to 33.3 N/mm (190 lb-f/in). All individual values and sub-ranges from greater than or equal to 33.3 N/mm (190 lb-f/in). are included herein and disclosed herein; for example, the tear strength of the inventive composition can be from greater than or equal to 33.3 (190), 35.0 (200), 36.8 (210) or 38.5 (220), 45.5 (260), 49.0 (280), 87.6 (500) N/mm (lb-f/in).
  • thermoplastic vulcanizate composition of the instant invention comprises: (A) selecting a first component comprising a first propylene-based polymer selected from the group consisting of (i) propylene/a-olefin copolymers comprising from 1 to 20 wt% ⁇ -olefin and characterized by a g' ratio of less than1, measured at interpolymer number average molecular weight (Mn), an MFR (2.16kg @ 230°C) greater than or equal to 0.01, a density greater than or equal to 0.850 g/cc, and a molecular weight distribution, Mw/Mn, less than 4, and (ii) combinations thereof and; (B) selecting a second component selected from the group consisting of curable or vulcanizable rubbers, having a density from 0.85 to 0.88 g/cc, I 2 from 0.0001 to 5 g/10 min, and a Mooney viscosity from 5 to 400, and combinations thereof; wherein at least one of the rubber
  • the inventive thermoplastic vulcanizate compositions may be prepared by any suitable method for mixing of rubbery polymers including mixing on a rubber mill or in internal mixers such as a Banbury mixer.
  • the conventional compounding ingredients are incorporated, may include one or more types of carbon black, additional extender oil, other fillers such as clay, silica, tackifiers, waxes, bonding resins, zinc oxide, antioxidants, antiozonants, processing aids, and the cure active agents, and pigments.
  • it is preferred to add the curing agents in a second stage of compounding which may be on a rubber mill or in an internal mixer operated at a temperature, preferably not in excess of about 60°C.
  • the compounds are cured in a conventional manner by heating from 5 to 60 minutes at temperatures of from 150 to 200°C to form novel elastomeric vulcanizates having useful properties.
  • Dynamic vulcanization is a process whereby a blend of plastic, rubber and rubber curative is masticated while curing the rubber.
  • the term “dynamic” indicates the mixture is subjected to shear forces during the vulcanization step as contrasted with “static” vulcanization wherein the vulcanizable composition is immobile (in fixed relative space) during the vulcanization step.
  • One advantage of dynamic vulcanization is that elastoplastic (thermoplastic elastomeric) compositions may be obtained when the blend contains the proper proportions of plastic and rubber.
  • inventive compositions may be used in a variety of applications requiring high performance (tensile strength, tensile set, tear strength and processability), such as tires, hoses, belts, gaskets, moldings and molded parts. They are also useful for modification of thermoplastic resins, in particular, thermoplastic polymer resins.
  • the compositions can be blended with thermoplastic resins to make rubber modified thermoplastic resin by using conventional mixing equipment. The properties of the modified thermoplastic resin depend upon the amount of thermoplastic elastomer composition blended.
  • the inventive compositions are used to form 11.5 ⁇ m (.452mil) or 11.7 ⁇ m (.462 mil) calendared sheets, thermoplastic sheets heat welded into membranes, pond liners, and roofing membranes.
  • component A is a propylene/ethylene copolymer with long chain branching, having an MFR of 2
  • component B is an EPDM polymer, commercially available as NORDEL IP 4770, available from The Dow Chemical Company
  • component C is a comparative propylene-based polymer, specifically, a propylene homopolymer and/or propylene/olefin copolymer (as specified in the following Tables) which does not exhibit
  • component D is a curing agent, selected from a phenolic resin, available from the SI Group under the name SP-1045, ZnO and SnCl 2 from Sinopharm Chemical Reagent Co., Ltd. (Shanghai, China)
  • component F is a paraffinic oil.
  • Compression molded samples were formed by compressing the cooled and granulated compositions at about 190 °C for about three minutes, followed by cooling using forced air. Following compression molding, the plaques were conditioned at room temperature (23 °C) for about 24 hours after which samples were cut into 15.2 x 15.2 x.32 cm plaques.
  • the compression molding technique described in ASTM D4703 was used for preparation of the sample plaques (ASTM D4703 also provides a test for test for density but, in this case, that test method was used solely for the plaque preparation).
  • the compounding process was also performed using an extruder according to the following: Components A,B,C, and F were charged to the extruder; oil was added; the phenolic curing agent (such as SP1055) was fed via a side arm feeder at a point along the extruder barrel such that all other ingredients have been intimately mixed prior to the phenolic curing agent feed.
  • the phenolic curing agent such as SP1055
  • non halogenated phenolic curatives such as SP1045
  • the halogen donator such as, stannous chloride
  • the extruder or mixer should be operated so that the temperature profile within the zones of the extruder preferably does not exceed 220°C. The melt was then cooled and pelletized.
  • inventive compositions can be used to produce a thermoplastic vulcanizate composition in a one step process either in a batch process (e.g. via Brabender) or via a continuous compounding process (e.g. twin screw).
  • compositions of Inventive Examples (Inv.Ex. 1-6) and Comparative Examples (Comp. Ex. A-F) shown in Tables 1-3 below were prepared using the following sample preparation method.
  • the extruded samples were formed into compression molded plaques at about 190 °C for about three minutes and cooled by cold press at room temperature (23 °C) for 5 min.
  • SANTOPRENE 201-64 available from Advanced Elastomer System is a curable or vulcanizable rubber comprising an EPDM interpolymer, a thermoplastic homopolypropylene, a filler and an oil. Comparative Example A is SANTOPRENE 201-64 with no first propylene-based polymer. Table 1 Comp. Ex. A (phr) Inv. Ex. 1 (phr) Comp. Ex. B (phr) Inv. Ex. 2 (phr) Comp. Ex. C (phr) Inv. Ex. 3 (phr) Comp. Ex.
  • the Inventive Examples which comprise a first propylene-based polymer characterized by a g' ratio of less than 1 have much higher tensile strength and generally improved mechanical properties than the Comparative Examples which comprise a first propylene-based polymer characterized by a g' ratio of greater than 1.
  • Inventive Example 1 has improved tensile strength at break, tear strength and elongation at break over Comparative Example B.
  • the amount of the propylene-based polymer is increased from 10 phr to 30 phr, the improved performance of Inventive Example 2 over Comparative Example C is seen for each of the tensile strength at break, tear strength and elongation at break properties.
  • Test methods utilized in characterizing the components of the Inventive and Comparative Examples include the tests described below.
  • the samples used for testing tensile strength, elongation at break, and tensile set were compression molded at 190°C and 10MPa.
  • the molten materials were then quenched in a press equilibrated at room temperature.
  • the chromatographic system used is a Polymer Laboratories Model PL-210.
  • the column and carousel compartments were operated at 145°C.
  • Four Polymer Laboratories 20-um Mixed-A LS columns were used, with a solvent of 1,2,4 Trichlorobenzene (TCB).
  • TCB 1,2,4 Trichlorobenzene
  • the samples were prepared at a concentration of 0.1 g of polymer in 50 ml of solvent.
  • the solvent contained 200 ppm of the antioxidant butylated hydroxytoluene (BHT). Samples were prepared by agitating lightly for 1-2 hours at 160°C.
  • the injection volume was 200 microliters and the flow rate was 1.0 ml/min.
  • Melt index (I 2 ) of an ethylene-based polymer is measured in accordance with ASTM D-1238-04, condition 190°C/2.16 kg.
  • Melt index (I 5 ) of an ethylene-based polymer is measured in accordance with ASTM D-1238-04, condition 190°C/5.0 kg.
  • Melt index (I 10 ) of an ethylene-based polymer is measured in accordance with ASTM D-1238-04, condition 190°C/10.0 kg.
  • High load melt index (I 21 ) of an ethylene-based polymer is measured in accordance with ASTM D-1238-04, condition 190°C/21.0 kg.
  • the melt flow rate (MFR) is measured in accordance with ASTM D-1238-04, condition 230°C/2.16 kg.
  • Shore A hardness was measured per ASTM D2240 on injection molded plaques of 0.32 cm thickness. This test method permits hardness measurements based on either initial indentation or indentation after a specified period of time, or both. As used herein, the indentation was measured at a specified time of 10 seconds.
  • Tensile strength and elongation at break was measured using ASTM D 1708 which is a micro-tensile method with a pull rate of 12.7 cm (5 inches)/minute in the flow direction of the injection molded plaque.
  • the dimensions of the injection molded plaque were 101.6 mm x 152.4 x 3.2 mm.
  • Polymer Mooney viscosity (ML 1+4 at 125°C) was measured in accordance with ASTM 1646-04, with a one minute preheat time and a four minute rotor operation time.
  • the instrument is an Alpha Technologies Rheometer MDR.
  • Density was measured according to ASTM D-792.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Processes Of Treating Macromolecular Substances (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

Claims (12)

  1. Une composition de vulcanisat thermoplastique constituée essentiellement :
    de 5 % en poids à 95 % en poids, rapporté au poids total de la composition de vulcanisat thermoplastique, d'un premier constituant comprenant un premier polymère à base de propylène, ledit premier polymère à base de propylène étant un copolymère propylène/a-oléfine comprenant de 1 à 20 % en poids d'a-oléfine et caractérisé par un rapport g' inférieur à 1, mesuré à la masse moléculaire moyenne en nombre de l'interpolymère (Mn), un IFC (2,16 kg à 230 °C) supérieur ou égal à 0,01, une masse volumique supérieure ou égale à 0,850 g/cm3, et une distribution des masses moléculaires, Mw/Mn, inférieure ou égale à 3,5, et
    de 5 % en poids à 95 % en poids, rapporté au poids total de la composition de vulcanisat thermoplastique, d'un deuxième constituant, le deuxième constituant comprenant un interpolymère de monomère éthylène-propylène-diène ayant une masse volumique de 0,85 à 0,88 g/cm3, un I2 de 0,001 à 5 g/10 min, et une viscosité Mooney de 5 à 400, et des combinaisons de ceux-ci ; ledit deuxième constituant étant vulcanisable ;
    la composition de vulcanisat thermoplastique ayant une résistance à la traction à la rupture supérieure ou égale à 8 MPa et une résistance au déchirement à 23 °C d'au moins 33,3 N/mm (190 lb-pi/po).
  2. La composition de vulcanisat thermoplastique selon la revendication 1, comprenant en outre un ou plusieurs additifs sélectionnés dans le groupe constitué de pigments colorés, de stabilisateurs, d'agents protecteurs, d'ignifugeants, d'auxiliaires de traitement, d'adhésifs, d'agents collants, de plastifiants, de cires, et de fibres discontinues.
  3. La composition de vulcanisat thermoplastique selon la revendication 1, comprenant en outre une ou plusieurs charges.
  4. Un procédé pour fabriquer une composition de vulcanisat thermoplastique constituée essentiellement :
    de la sélection d'un premier constituant, ledit premier constituant étant un premier polymère à base de propylène sélectionné dans le groupe constitué (i) de copolymères propylène/a-oléfine comprenant de 1 à 20 % en poids d'a-oléfine et caractérisé par un rapport g' inférieur à 1, mesuré à la masse moléculaire moyenne en nombre de l'interpolymère (Mn), un IFC (2,16 kg à 230 °C) supérieur ou égal à 0,01, une masse volumique supérieure ou égale à 0,850 g/cm3, et une distribution des masses moléculaires, Mw/Mn, inférieure ou égale à 3,5, et (ii) de combinaisons de ceux-ci ;
    de la sélection d'un deuxième constituant, le deuxième constituant comprenant un interpolymère de monomère éthylène-propylène-diène, ayant une masse volumique de 0,85 à 0,88 g/cm3, un I2 de 0,001 à 5 g/10 min, et une viscosité Mooney de 5 à 400, et des combinaisons de ceux-ci ; ledit deuxième constituant étant vulcanisable ; et
    du mélange des premier et deuxième constituants dans des conditions de vulcanisation dynamique afin de former la composition de vulcanisat thermoplastique ;
    la composition de vulcanisat thermoplastique ayant une résistance à la traction à la rupture supérieure ou égale à 8 MPa et une résistance au déchirement à 23 °C d'au moins 33,3 N/mm (190 lb-pi/po).
  5. Un article constitué d'une ou de plusieurs compositions de vulcanisat thermoplastique de n'importe laquelle des revendications 1 à 3.
  6. La composition de vulcanisat thermoplastique selon la revendication 1 dans laquelle le premier polymère à base de propylène a un rapport g' inférieur à 0,85, mesuré à la masse moléculaire moyenne en nombre de l'interpolymère (Mn).
  7. La composition de vulcanisat thermoplastique selon la revendication 1 dans laquelle le premier polymère à base de propylène a un rapport g' inférieur à 0,80, mesuré à une masse moléculaire moyenne en nombre d'interpolymère (Mn).
  8. La composition de vulcanisat thermoplastique selon la revendication 1 dans laquelle le premier polymère à base de propylène comprend au moins 80 pour cent en poids (% en poids) d'unités dérivées de propylène, et entre 1 et 20 % en poids d'unités dérivées d'éthylène.
  9. La composition de vulcanisat thermoplastique selon la revendication 1 dans laquelle le premier polymère à base de propylène est caractérisé par une dérive de composition relative de moins de 50 %.
  10. La composition de vulcanisat thermoplastique selon la revendication 1 dans laquelle le premier polymère à base de propylène est caractérisé par une dérive de composition relative de moins de 40 %.
  11. La composition de vulcanisat thermoplastique selon la revendication 1 dans laquelle le premier polymère à base de propylène est caractérisé par des segments de chaîne propylène ayant un indice d'isotacticité de triades de chaîne d'au moins 70 pour cent en moles.
  12. La composition de vulcanisat thermoplastique selon la revendication 1 dans laquelle le premier polymère à base de propylène est caractérisé par des segments de chaîne propylène ayant un indice d'isotacticité de triades de chaîne d'au moins 80 pour cent molaire.
EP10861392.8A 2010-12-30 2010-12-30 Composition de vulcanisat thermoplastique, son procédé de production, et articles fabriqués à partir de celle-ci Active EP2658919B1 (fr)

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WO2012088689A1 (fr) 2012-07-05
KR20130131419A (ko) 2013-12-03
CN103403086A (zh) 2013-11-20
CN103403086B (zh) 2016-12-07
BR112013016647B1 (pt) 2020-04-07
BR112013016647A2 (pt) 2017-07-11
KR101843217B1 (ko) 2018-03-28
US20130324658A1 (en) 2013-12-05
JP5764669B2 (ja) 2015-08-19
JP2014501308A (ja) 2014-01-20
US9309396B2 (en) 2016-04-12
EP2658919A1 (fr) 2013-11-06

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